1. Field of the Invention
[0001] The present invention relates to opaque security documents that can be verified on
their authenticity and are protected against counterfeiting by photo-copying.
2. Background of the Invention
[0002] Security documents that must be verifiable on their authenticity are e.g. all kinds
of identification documents such as passports, visas, identity cards, driver licenses,
bank cards, credit cards, security entrance cards, and further value-documents such
as banknotes, shares, bonds, certificates, cheques, lottery tickets and all kinds
of entrance tickets such as airplane tickets and railroad season-tickets.
[0003] Nowadays, by the availability of markedly improved black-and-white and color copiers
it becomes more and more easy to copy documents at high quality hardly to distinguish
from the originals.
[0004] To protect the above mentioned documents against fraudulent alterations and reproduction
by photo-copying different techniques are used such as the melt-laminating or glueing
thereto of preprinted plastic overlayers; the printing with special inks; the application
of coatings or layers for example loaded with magnetic or fluorescent pigments; coloring
or metallizing the substrate of the documents; incorporating holograms: applying fine
line printing, watermarks, fibers, security threads, light diffraction marks, liquid
crystal marks and/or substances called nacreous, iridiscent or interference pigments.
[0005] In a particular case disclosed in US-P 4,151,666 light-transmissive pigments serving
as diffuse reflectors are applied by printing to form a verification pattern in a
laminated identification card (I.D. card). In the specification of the same US-P the
use of nacreous pigments in verification patterns has been described. Nacreous pigments,
also called pearlescent pigments have light-reflection characteristics that change
as a function of the viewing or copying angle. The effect of changing color with viewing
angle makes that nacreous pigments represent a simple and convenient matter to built
in a verification feature associated with a non-copyable optical property.
3. Objects and Summary of the Invention
[0006] It is an object of the present invention to provide opaque security documents incorporating
a photograph and containing a verification feature that can not be copied by photographic
techniques and wherein there is no need for specialized devices or conditions to verify
the document on its authenticity.
[0007] It is more particularly an object of the present invention to provide opaque security
documents containing at least one photograph obtained by means of the silver complex
or dye diffusion transfer process in combination with interference pigments applied
by coating before the photograph is formed.
[0008] It is a special object of the present invention to provide an opaque security document
containing a portrait in combination with a plurality of interference pigments of
different color for easy verfication by the naked eye of the security document involved.
[0009] Other objects and advantages of the present invention will become clear from the
further description and examples.
[0010] In accordance with the present invention there is provided a document containing
a photograph obtained by the silver complex or dye diffusion transfer process in an
image receiving layer, characterized in that said document contains light interference
pigments uniformly distributed in said image receiving layer, and/or in a layer overlaying
or underlying said image receiving layer, said layer(s) being present on an opaque
support.
[0011] By "opaque support" in the document according to the present invention has to be
understood a support having a visible light-blocking capacity of at least 70 %, not
excluding supports that have inherently a color or contain colorants, e.g. dyes or
pigments.
[0012] Said layers containing said uniformly distributed interference pigments may be present
at both sides of said opaque support.
4. Detailed Description of the Invention
[0013] Nacreous or pearlescent pigments being interference pigments were originally named
for their simulation of pearly luster.
[0014] Interference pigments are in the form of light-reflecting crystal platelets of appropriate
thickness to produce color by interference. These pigments exhibit a color play that
verges on iridiscence and under a given angle of reflection will allow only the copying
of a single color, whereas other colors appear under different angles of reflection,
in other words these pigments show another color to the human eye depending on the
observation angle.
[0015] Very good anticopying results are obtained with synthetic inorganic interference
pigments chief among which are titanium dioxide-coated mica or other metal-oxide coated
pigments in which the metal oxide has preferably a refractive index comparable with
the refractive index of TiO
2, e.g. ZrO
2, Fe
2O
3 or Cr
2O
3.
[0016] The platelets of metal oxide coated mica pigments have three layers in such a way
that on each of the broad faces of the mica platelets a very thin coating of metal
oxide is present.
[0017] The more brilliant interference pigments approach metallic luster, an effect that
is enhanced by the presence of absorption colorants. TiO
2-mica readily lends itself to incorporation of absorption colorants. Ferric oxide
(Fe
2O
3) added to the TiO
2 layer, for example imparts a yellow color which in conjunction with a yellow interference
color creates gold. When Fe
2O
3 is used in place of TiO
2 as the oxide coating on mica, these pigments have a yellow-red absorption color because
of the inherent color of the Fe
2O
3. They range from bronze to deep copper-red and have a metallic luster.
[0018] The preparation of such kind of pigments is described in "Nacreous (Pearlescent)
Pigments and Interference Pigments by L.M. Greenstein Henry L. Mattin Laboratories
Reprinted from Pigment Handbook, Vol. I, Properties and Economics, Second Edition,
Edited by Peter A. Lewis, (1988) by permission of John Wiley & Sons, Inc. The Mearl
Corporation, 41 East 42nd Street, New York, N.Y. 100017.
[0019] Mica pigments serving as a substrate of the interference coatings are a group of
hydrous aluminum silicate minerals with platy morphology and perfect basal (micaceous)
cleavage. Examples of suitable micas are e.g. muscovite KAl
2(AlSi
3O
10)(OH)
2, paragonite NaAl
2(AlSi
3O
10)(OH)
2, phlogopite K(Mg.Fe)(AlSi
3O
10)(OH)
2, biotite K(Fe,Mg)(AlSi
3O
10)(OH)
2 and lepidolite K(Li.Al)
2.5-3.0(Al
1.0-0.5Si
3.0-3.5O
10)(OH)
2 etc..
[0020] Details about the application of metal and/or metal oxide coatings on the mica platelets
are further given in US-P 3,087,827, 4,434,010 and 5,059,245 and in published EP-A-45
851, EP-A-313 280, DE-A-11 65 182, DE-A-32 37 264, DE-A-38 25 702 and DE-A-36 17 430
and DE-OS 41 41 069.
[0021] In a preferred embodiment according to the present invention interference pigments
having a composition as described in published German patent application DE-OS 41
41 069 are used. Said interference pigments, called "Glanzpigmente" according to said
DE-OS are composed of silicate platelets coated with either :
A) a first layer of highly refractive metal oxide, and
B) a second black layer essentially consisting of metallic iron, molybdenum and/or
wolfram, or coated with :
A) a first layer of highly refractive metal oxide, and
B) a second black layer essentially consisting of carbon or metal, and
C) a third layer of highly refractive metal oxide.
By the presence of a semi-transparent carbon layer said platelets have a high chemical
resistance. The carbon layer is obtained by thermal decomposition of oxygen-containing
hydrocarbon compounds which for each two carbon atoms contain at least one oxygen
atom e.g. as in carbohydrates such as sorbitol.
The metal layer B) can be formed in a medium of inert gas from in-gas-phase-decomposable
metal compounds, e.g. metal carbonyl compounds, and the metal oxide layers A) and
C) are formed by decomposition in gas phase of volatile metal compounds in the presence
of oxygen water vapour or mixtures thereof.
[0022] The first layer A) consists e.g. of the oxides of titanium, zirconium, tin and/or
iron.
[0023] Mica platelets double-side coated with one or more metal oxide layers for use as
interference pigments are commercially available e.g. under the tradenames IRIODINE
(E. Merck, Darmstadt), FLONAC (Kemira Oy, Pori, Finland), MEARLIN (The Mearl Corporation,
New York, U.S.A.) and PALIOSECURE (BASF, Germany). Under these tradenames interference
pigments showing violet, red, green and blue colors are available on the market.
[0024] Preferred interference platelet-type pigments for use according to the present invention
have a largest surface diameter preferably between 5 and 200 µm and more preferably
of 25 µm to 30 µm. The thickness of the platelet-type interference pigments is preferably
between 0.1 µm and 0.6 µm and more preferably between 0.2 µm and 0.4 µm.
[0025] In accordance with a preferred embodiment particularly good anti-copying security
is obtained by means of an opaque document wherein said uniformly distributed interference
pigments of a particular color are present in combination with a printed pattern containing
interference pigments of a color different from the color of the uniformly distributed
interference pigments when viewed under the angle of reflection under which photocopying
could take place.
[0026] The "copying angle" is the angle, usually 90°, formed by the information-containing
light rays and the copying material.
[0027] In accordance with another embodiment there is provided an opaque document wherein
said uniformly distributed interference pigments are present in conjunction with different
and pattern-wise printed interference pigments on a background having a color substantially
the same as the color, e.g. yellow, reflected by said pattern-wise printed interference
pigments under the angle of reflection under which photocopying could take place.
Hereby the pattern of the pattern-wise printed interference pigments becomes undetectable
against the image background for the copying machine, but is still visible in the
document under a viewing angle different from the copying angle.
[0028] In accordance with a further embodiment there is provided an opaque document wherein
said uniformly distributed interference pigments are present in combination with pattern-wise
printed colored light absorbing substances (colored pigments or dyes), and/or white
light-diffusing pigments.
[0029] The layer containing the uniformly distributed interference pigments may be applied
by coating techniques operating with a coating liquid containing said pigments in
dispersed form and a dissolved binding agent or containing said pigments dispersed
together with a binding agent in the form of a latex. After coating the solvent or
dispersing liquid, e.g. water, is removed by evaporation. Any coating technique for
the application of thin liquid layers may be used as is known e.g. from the field
of the manufacture of photographic silver halide emulsion layer materials, e.g. doctor
blade coating, gravure roller coating, meniscus coating, air knife coating, slide
hopper coating and spraying.
[0030] According to a special coating technique the interference pigments are applied in
a radiation-curable binder or binder system wherein e.g. monomers act as solvent for
polymers or prepolymers as described e.g. in published EP-A 0 522 609, so that after
coating of the liquid coating composition no solvent has to be evaporated.
[0031] In accordance with a particular embodiment the uniformly distributed interference
pigments are applied in a layer that is transferred by a stripping-off procedure to
built the document of the present invention. Such procedure is described in published
EP-A 0 478 790 but is applied therein for controlling the whiteness of an image present
on a permanent support using for the stripping-off and transfer procedure a temporary
support coated with a wet-strippable non-photosensitive layer containing fluorescent
whitening agent(s) in a hydrophilic colloid binder.
[0032] According to a special embodiment the interference pigments applied in the form of
a pigment-transfer-foil wherefrom by hot transfer the pigments are transferred uniformly
onto the substrate of the security document.
[0033] Still another coating technique suited for uniformly applying said pigments is by
dry powder-spraying optionally on a hot-melt resin layer wherein they are impregnated
by pressure and heat. On top of the pigments an adhesive, e.g. wax may be applied
to improve adherence to the selected substrate. That substrate may have hydrophilic
or hydrophobic surface properties.
[0034] Spray-coating may be applied for covering the whole surface of the substrate or only
a part thereof producing "light interference rainbow-effects". By using varying mixtures
of different interference pigments the intensity of one color can be made to decrease
gradually while an increasing color intensity of another pigment comes up. The human
eye will see the rainbow effect varying according to the perception angle and will
recognize the basic color of each of the sprayed pigments, but a photocopier operating
with a fixed copying angle will only reproduce, say a single yellowish-brown color
and not the colors of the interference pigments that can be seen under different inspection
angles.
[0035] The interference pigments can be used for pigmenting a commercial coating varnish
which may then be used for pre-coating a security document substrate, e.g. opaque
resin film or paper. The coating may proceed with common varnishing or impregnation
machinery instead of using printing presses.
[0036] As already mentioned herein the uniformly applied interference pigments are advantageously
combined with image-wise or pattern-wise interference pigments of another color.
[0037] The image-wise or pattern-wise application of interference pigments proceeds by printing
with an ink containing said pigments. Suited printing processes are e.g. planographic
offset printing, gravure printing, intaglio printing, screen printing, flexographic
printing, relief printing, tampon printing, ink jet printing and toner-transfer printing
from electro(photo)graphic recording materials.
[0038] For use in printing on hydrophilic layers or substrates the ink contains for example
a 15 to 20 % by weight mixture of the interference pigments in a solution of cellulose
nitrate in a polyethylene ether. Such ink has a good adherence on hydrophilic colloid
layers such as gelatin-containing layers used in DTR-recording materials. Said ink
is advantageously applied with a commercial screen press using a polyester screen
with a 77 and 55 mesh. The interference colors gradually appear on drying the ink.
[0039] Thus applied ink patterns on a hydrophilic image-receiving layer for DTR-image production
remain unchanged during DTR-processing.
[0040] The presence of the interference pigments in one of the layers of the opaque security
document does not affect the possibility to print thereon further graphic or alpha-numerical
information by any known printing technique.
[0041] For easy visual verification the interference pigments are present preferably in
a coverage of 0.3 g/m
2 to 10 g/m
2 and more preferably in a coverage between 0.7 g/m
2 and 3 g/m
2 in the above mentioned silver-type DTR and dye diffusion transfer materials, either
in the image-receiving layer itself and/or in a waterpermeable top layer and/or in
a subbing layer covering the support.
[0042] The presence of a dried water-impermeable ink pattern on the image-receiving layer
blocks DTR-image formation. Thereby it is possible to arrange e.g. fine line patterns
such as guilloches in the photograph creating that way an additional security feature.
[0043] The printing of an interference pigment-containing pattern may proceed on a substrate
already covered e.g. by a hologram, light-diffraction pattern, metallic pattern that
can be viewed throught the printed pattern so that the properties of the interference
pigments are added thereto.
[0044] The printed pattern containing interference pigments forms no obstacle for a good
adherence with laminated plastic resinous covering material. By proper selection of
the binder of the ink it can be co-melted with the resin material laminated thereto.
[0045] According to a particular embodiment the interference pigment-containing ink is applied
on a temporary support, e.g. polystyrene support, wherefrom the ink layer can be stripped
off and transferred to a permanent support, e.g. a glued and preprinted substrate
of a security document. The ink layer, applied overall or pattern-wise, after leaving
the temporary support covers underlying pre-printed data on the permanent support.
For preventing fraudulent copying these data have the same color as the interference
pigment layer when seen under the copying angle. Insufficient image contrast is available
so that copying of the pre-printed data is no longer possible. By applying a dried
interference pigment-containing ink layer that is translucent the underlying data
can be visually inspected therethrough by altering the perception angle.
[0046] In accordance with the preceding embodiment a security document according to the
present invention, e.g. serving as I.D. card, is preferably in the form of a laminate
in which the information-containing layer(s) are sealed between protective resinous
sheets. I.D. card laminates may be built up as described e.g. in US-P 4,101,701, US-P
4,762,759, US-P 4,902,593, published EP-A 0 348 310 and published EP-A 0 462 330.
By lamination tamper-proof documents are produced which do not allow the opening of
the laminate without damaging the image contained therein. The destruction of the
seal will leave visual fraude traces on the security document.
[0047] In accordance with a first mode in the opaque security document according to the
present invention a black-and-white photograph in the form of a silver image is formed
by the silver salt diffusion transfer process, called herein DTR-process. According
to said process dissolved silver halide salt is transferred imagewise in a special
image receiving layer, called development nuclei containing layer, for reducing therein
transferred silver salt, said development nuclei containing layer contains itself
and/or in an overlaying and/or an underlaying layer uniformly distributed therein
said interference pigments.
[0048] The principles of the DTR-process are described in U.S. patent No. 2,352,014 of André
Rott, issued June 20, 1944. According to said process silver complexes are image-wise
transferred by diffusion from a silver halide emulsion layer to an image-receiving
layer, where they are converted, in the presence of development nuclei, into a silver
image. For this purpose, an image-wise exposed silver halide emulsion layer is developed
by means of a developing substance in the presence of a so-called silver halide solvent.
In the exposed parts of the silver halide emulsion layer the silver halide is developed
to metallic silver so that it cannot dissolve anymore and consequently cannot diffuse.
In the non-exposed parts of the silver halide emulsion layer the silver halide is
converted into soluble silver complexes by means of a silver halide complexing agent,
acting as silver halide solvent, and said complexes are transferred by diffusion into
an image-receiving layer being in waterpermeable contact with said emulsion layer
to form by the catalytic action of said development nuclei, in so-called physical
development, a silver-containing image in the image-receiving layer.
[0049] More details on the DTR-process can be found in "Photographic Silver Halide Diffusion
Processes" by A. Rott and E. Weyde, Focal Press, London, New York (1972).
[0050] In accordance with a second mode in the opaque security document according to the
present invention a color photograph in the form of one or more dye images is formed
by the dye diffusion transfer process (dye DTR-process) wherein the image-wise transfer
of dye(s) is controlled by the development of (a) photo-exposed silver halide emulsion
layer(s), and wherein dye(s) is (are) transferred imagewise in a special image receiving
layer, called mordant layer, for fixing the dyes, said mordant layer and/or an overlaying
and/or an underlaying layer containing uniformly distributed therethrough said interference
pigments.
[0051] Dye diffusion transfer reversal processes are based on the image-wise transfer of
diffusible dye molecules from an image-wise exposed silver halide emulsion material
into a waterpermeable image-receiving layer containing a mordant for the dye(s). The
image-wise diffusion of the dye(s) is controlled by the development of one or more
image-wise exposed silver halide emulsion layers, that for the production of a multicolor
image are differently spectrally sensitized and contain respectively a yellow, magenta
and cyan dye molecules. A survey of dye diffusion transfer imaging processes has been
given by Christian C. Van de Sande in Angew. Chem. - Ed. Engl.
22 (1983) n° 3, 191-209 and a particularly useful process is described in US-P 4,496,645.
[0052] For use in dye diffusion transfer photography the type of mordant chosen will depend
upon the dye to be mordanted. If acid dyes are to be mordanted, the image-receiving
layer being a dye-mordanting layer contains basic polymeric mordants such as polymers
of amino-guanidine derivatives of vinyl methyl ketone such as described in US-P 2,882,156,
and basic polymeric mordants and derivatives, e.g. poly-4-vinylpyridine, the metho-p-toluene
sulphonate of poly-2-vinylpyridine and similar compounds described in US-P 2,484,430,
and the compounds described in the published DE-A 2,009,498 and 2,200,063. Other mordants
are long-chain quaternary ammonium or phosphonium compounds or ternary sulphonium
compounds, e.g. those described in US-P 3,271,147 and 3,271,148,, and cetyltrimethyl-ammonium
bromide. Certain metal salts and their hydroxides that form sparingly soluble compounds
with the acid dyes may be used too. The dye mordants are dispersed or molecularly
divided in one of the usual hydrophilic binders in the image-receiving layer, e.g.
in gelatin, polyvinylpyrrolidone or partly or completely hydrolysed cellulose esters.
[0053] In US-P 4,186,014 cationic polymeric mordants are described that are particularly
suited for fixing anionic dyes, e.g. sulphinic acid salt dyes that are image-wise
released by a redox-reaction described e.g. in in published EP-A 0,004,399 and US-P
4,232,107.
[0054] The DTR process can be utilized for reproducing line originals e.g. printed documents,
as well as for reproducing continuous tone originals. e.g. portraits.
[0055] By the fact that the DTR-image is based on diffusion transfer of imaging ingredients
the image-receiving layer and optionally present covering layer(s) have to be waterpermeable.
[0056] The reproduction of black-and-white continuous tone images by the DTR-process requires
the use of a recording material capable of yielding images with considerable lower
gradation than is normally applied in document reproduction to ensure the correct
tone rendering of continuous tones of the original. In document reproduction silver
halide emulsion materials are used which normally mainly contain silver chloride.
Silver chloride not only leads to a more rapid development but also to high contrast.
[0057] In U.S. patent. No. 3,985,561, to be read in conjunction herewith, a light-sensitive
silver halide material is described wherein the silver halide is predominantly chloride
and this material is capable of forming a continuous tone image on or in an image-receiving
material by the diffusion transfer process.
[0058] According to said U.S. patent a continuous tone image is produced by the diffusion
transfer process in or on an image-receiving layer through the use of a light-sensitive
layer which contains a mixture of silver chloride and silver iodide and/or silver
bromide dispersed in a hydrophilic colloid binder e.g. gelatin, wherein the silver
chloride is present in an amount of at least 90 mole % based on the total mole of
silver halide and wherein the weight ratio of hydrophilic colloid to silver halide,
expressed as silver nitrate, is between 3:1 and about 10:1 by weight.
[0059] With these light-sensitive materials successful reproduction of continuous tone images
can be obtained probably as a result of the presence of the indicated amounts of silver
iodide and/or silver bromide and of the defined high ratio of hydrophillic colloid
to silver halide.
[0060] According to U.S. patent No. 4,242,436 likewise to be read in conjunction herewith,
the reproduction of continuous tone images can be improved by developing the photographic
material with a mixture of developing agents comprising an o-dihydroxybenzene, e.g.
catechol, a 3-pyrazolidinone e.g. a 1-aryl-3-pyrazolidinone and optionally a p-dihydroxybenzene,
e.g. hydroquinone, the molar amount of the o-dihydroxybenzene in said mixture being
larger than the molar amount of the 3-pyrazolidinone, and the p-dihydroxybenzene if
any being present in a molar ratio of at most 5 % with respect to the o-dihydroxybenzene.
[0061] Suitable development nuclei for use in the above mentioned physical development in
the image receiving layer are e.g. noble metal nuclei e.g. silver, palladium, gold,
platinum, sulphides, selenides or tellurides of heavy metals such as Pd, Ag, Ni and
Co. Preferably used development nuclei are colloidal PdS, Ag
2S or mixed silver-nickelsulphide particles. The amount of nuclei used in the image
receiving layer is preferably between 0.02 mg/m
2 and 10 mg/m
2.
[0062] The image receiving layer comprises for best imaging results the physical development
nuclei in the presence of a protective hydrophilic colloid, e.g. gelatin and/or colloidal
silica, polyvinyl alcohol etc..
[0063] The transfer behaviour of the complexed silver largely depends on the thickness of
the image-receiving layer and the kind of binding agent or mixture of binding agents
used in the nuclei containing layer. In order to obtain a sharp image with high spectral
density the reduction of the silver salts diffusing into the image receiving layer
must take place rapidly before lateral diffusion becomes substantial. An image-receiving
material satisfying said purpose is described in US-P 4,859,566.
[0064] An image-receiving material of this type is very suitable for use in connection with
the present invention and contains a water-impermeable support coated with (1) an
image-receiving layer containing physical development nuclei and interference pigments
dispersed in a waterpermeable binder and (2) a waterpermeable top layer free from
development nuclei and containing a hydrophilic colloid, in such a way that :
(i) the total solids coverage of said two layers (1) and (2) is e.g. at most 2 g/m2,
(ii) in layer (1) the coverage of the nuclei is in the range of 0.1 mg/m2 to 10 mg/m2, and the coverage of binder is in the range of 0.4 to 1.5 g/m2, and
(iii) in said top layer (2) the coverage of hydrophilic colloid is in the range of
0.1 to 0.9 g/m2.
[0065] The coating of said layers proceeds preferably with slide hopper coater or curtain
coater known to those skilled in the art.
[0066] According to a particular embodiment the nuclei containing layer (1) is present on
a nuclei-free underlying hydrophilic colloid undercoat layer or undercoat layer system
having a coverage in the range of 0.1 to 1 g/m
2 of hydrophilic colloid, the total solids coverage of layers (1) and (2) together
with the undercoat being at most 2 g/m
2. In connection with this embodiment the nacreous pigments may be also be included
in the undercoat layer or may be included therein instead of being present in the
nuclei containing layer.
[0067] The undercoat optionally incorporates substances that improve the image quality,
e.g. incorporates a substance improving the image-tone or the whiteness of the image
background. For example, the undercoat may contain a fluorescent substance, silver
complexing agent(s) and/or development inhibitor releasing compounds known for improving
image sharpness.
[0068] According to a special embodiment the image-receiving layer (1) is applied on an
undercoat playing the role of a timing layer in association with an acidic layer serving
for the neutralization of alkali of the image-receiving layer. By the timing layer
the time before neutralization occurs is established, at least in part, by the time
it takes for the alkaline processing composition to penetrate through the timing layer.
Materials suitable for neutralizing layers and timing layers are disclosed in Research
Disclosure July 1974, item 12331 and July 1975, item 13525.
[0069] In the image-receiving layer (1) and/or in said top layer (2) and/or in an alkali-neutralizing
undercoat gelatin is used preferably as hydrophilic colloid. In layer (1) gelatin
is present preferably for at least 60 % by weight and is optionally used in conjunction
with an other hydrophilic colloid, e.g. polyvinyl alcohol, cellulose derivatives,
preferably carboxymethyl cellulose, dextran, gallactomannans, alginic acid derivatives,
e.g. alginic acid sodium salt and/or watersoluble polyacrylamides. Said other hydrophilic
colloid may be used also in the top layer for at most 10 % by weight and in the undercoat
in an amount lower than the gelatin content.
[0070] The image-receiving layer and/or a hydrophilic colloid layer in water-permeable relationship
therewith may comprise a silver halide developing agent and/or silver halide solvent,
e.g. sodium thiosulphate in an amount of approximately 0.1 g to approximately 4 g
per m
2.
[0071] The image-receiving layer or a hydrophilic colloid layer in water-permeable relationship
therewith may comprise colloidal silica.
[0072] The image-receiving layer may contain as physical development accelerators, in operative
contact with the developing nuclei, thioether compounds such as those described e.g.
in DE-A-1,124,354; US-P 4,013,471; US-P 4,072,526 and in EP 26520.
[0073] According to a preferred embodiment the processing liquid and/or the DTR image-receiving
material contains at least one image toning agent. In said case the image toning agent(s)
may gradually transfer by diffusion from said image-receiving material into the processing
liquid and keep therein the concentration of said agents almost steady. In practice
such can be realized by using the silver image toning agents in a coverage in the
range from 1 mg/m
2 to 20 mg/m
2 in a hydrophilic waterpermeable colloid layer.
[0074] A survey of suitable toning agents is given in the above mentioned book of André
Rott and Edith Weyde, p. 61-65, preference being given to 1-phenyl-1H-tetrazole-5-thiol,
also called 1-phenyl-5-mercapto-tetrazole, tautomeric structures and derivatives thereof
such as 1-(2,3-dimethylphenyl)-5-mercapto-tetrazole,
1-(3,4-dimethylcyclohexyl)-5-mercapto-tetrazole,
1-(4-methylphenyl)-5-mercapto-tetrazole,
1-(3-chloro-4-methylphenyl)-5-mercapto-tetrazole,
1-(3,4-dichlorophenyl)-5-mercapto-tetrazole. Further particularly useful toning agents
are of the class of thiohydantoins and of the class of phenyl substituted mercapto-triazoles.
Still further toning agents suitable for use in accordance with the preferred embodiment
of the present invention are the toning agents described in published European patent
applications 218752, 208346, 218753 and US-P 4,683,189.
[0075] In the security documents according to the present invention the opaque support is
e.g. an opaque paper support or resin coated paper supports, e.g. polyolefin coated
paper and polyethylene coated paper of which the polyethylene layer may contain the
interference pigments or other opacity providing pigments such as white TiO
2 particles as described e.g. in published European patent application (EP-A) 0 324
192. The opaque supports reflecting white light may contain optical brightening agents.
[0076] Other opaque supports that may be used are resin supports containing in their resin
mass dispersed white pigments, e.g. TiO
2, or are such resin supports that contain said pigments dispersed in the resin mass
in the presence of light-straying microvoids as described e.g. in EP 349152. Organic
resins used for manufacturing said supports, e.g. by extrusion, are polycarbonate,
polyester, preferably polyethylene terephthalate, polystyrene and homo- and copolymers
of vinyl chloride. Further are mentioned cellulose esters e.g. cellulose triacetate.
[0077] The above mentioned DTR image-receiving materials may be used in conjunction with
any type of photosensitive material containing a silver halide emulsion layer. For
continuous tone reproduction the silver halide comprises preferably a mixture of silver
chloride, and silver iodide and/or silver bromide, at least 90 mole % based on the
total mole of the silver halide being silver chloride, and the ratio by weight of
hydrophilic colloid to silver halide expressed as silver nitrate is between 3:1 and
10:1.
[0078] The binder for the silver halide emulsion layer and other optional layers contained
on the imaging element is preferably gelatin. But instead of or together with gelatin,
use can be made of one or more other natural and/or synthetic hydrophilic colloids,
e.g. albumin, casein, zein, polyvinyl alcohol, alginic acids or salts thereof, cellulose
derivatives such as carboxymethyl cellulose, modified gelatin, e.g. phthaloyl gelatin
etc. The weight ratio in the silver halide emulsion layer of hydrophilic colloid binder
to silver halide expressed as equivalent amount of silver nitrate to binder is e.g.
in the range of 1:1 to 10:1, but preferably for continuous tone reproduction is between
3.5:1 and 6.7:1.
[0079] The silver halide emulsions may be coarse or fine grain and can be prepared by any
of the well known procedures e.g. single jet emulsions, double jet emulsions such
as Lippmann emulsions, ammoniacal emulsions, thiocyanate- or thioether-ripened emulsions
such as those described in US-P 2,222,264, 3,320,069, and 3,271,157. Surface image
emulsions may be used or internal image emulsions may be used such as those described
in US-P 2,592,250, 3,206,313, and 3,447,927. If desired, mixtures of surface and internal
image emulsions may be used as described in US-P 2,996,382.
[0080] The silver halide particles of the photographic emulsions may have a regular crystalline
form such as cubic or octahedral form or they may have a transition form. Regular-grain
emulsions are described e.g. in J. Photogr. Sci., Vol. 12, No. 5, Sept./Oct. 1964,
pp. 242-251. The silver halide grains may also have an almost spherical form or they
may have a tabular form (so-called T-grains), or may have composite crystal forms
comprising a mixture of regular and irregular crystalline forms. The silver halide
grains may have a multilayered structure having a core and shell of different halide
composition. Besides having a differently composed core and shell the silver halide
grains may comprise also different halide compositions and metal dopants inbetween.
[0081] The average size expressed as the average diameter of the silver halide grains may
range from 0.2 to 1.2 um, preferably between 0.2µm and 0.8µm, and most preferably
between 0.3µm and 0.6µm. The size distribution can be homodisperse or heterodispere.
A homodisperse size distribution is obtained when 95 % of the grains have a size that
does not deviate more than 30 % from the average grain size.
[0082] The emulsions can be chemically sensitized e.g. by adding sulphur-containing compounds
during the chemical ripening stage e.g. allyl isothiocyanate, allyl thiourea, and
sodium thiosulphate. Also reducing agents e.g. the tin compounds described in BE-A
493,464 and 568,687, and polyamines such as diethylene triamine or derivatives of
aminomethane-sulphonic acid can be used as chemical sensitizers. Other suitable chemical
sensitizers are noble metals and noble metal compounds such as gold, platinum, palladium,
iridium, ruthenium and rhodium. This method of chemical sensitization has been described
in the article of R.KOSLOWSKY, Z. Wiss. Photogr. Photophys.
Photochem. 46, 65-72 (1951).
[0083] The emulsions can also be sensitized with polyalkylene oxide derivatives, e.g. with
polyethylene oxide having a molecular weight of 1000 to 20,000, or with condensation
products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products
of hexitols, alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines,
aliphatic diamines and amides. The condensation products have a molecular weight of
at least 700, preferably of more than 1000. It is also possible to combine these sensitizers
with each other as described in BE-P 537,278 and GB-P 727,982.
[0084] The silver halide emulsion may be sensitized panchromatically to ensure reproduction
of all colors of the visible part of the spectrum or it may be orthochromatically
sensitized.
[0085] The spectral photosensitivity of the silver halide can be adjusted by proper spectral
sensitization by means of the usual mono- or polymethine dyes such as acidic or basic
cyanines, hemicyanines, oxonols, hemioxonols, styryl dyes or others, also tri- or
polynuclear methine dyes e.g. rhodacyanines or neocyanines. Such spectral sensitizers
have been described by e.g. F.M. HAMER in "The Cyanine Dyes and Related Compounds"
(1964) Interscience Publishers, John Wiley & Sons, New York.
[0086] The silver halide emulsions may contain the usual stabilizers e.g. homopolar or salt-like
compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles,
simple mercury salts, sulphonium mercury double salts and other mercury compounds.
Other suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes,
especially those substituted with hydroxy or amino groups. Compounds of this kind
have been described by BIRR in Z. Wiss. Photogr. Photophys. Photochem. 47, 2-27 (1952).
Other suitable stabilizers are i.a. heterocyclic mencapto compounds e.g. phenylmercaptotetrazole,
quaternary benzothiazole derivatives, and benzotriazole.
[0087] A survey of photographic silver halide emulsions and their preparation is given in
Research Disclosure December 1989, item 308119.
[0088] Processing of the image-wise exposed photographic silver halide emulsion layer proceeds
whilst in contact with an image receiving material according to the invention and
is accomplished using an alkaline processing liquid having a pH preferably between
9 and 13. The pH of the alkaline processing liquid may be established using various
alkaline substances. Suitable alkaline substances are inorganic alkali e.g. sodium
hydroxide, potassium carbonate or alkanolamines or mixtures thereof. Preferably used
alkanolamines are tertiary alkanolamines e.g. those described in EP-A-397925, EP-A-397926,
EP-A-397927, EP-A-398435 and US-P 4,632,896. A combination of alkanolamines having
both a pk
a above or below 9 or a combination of alkanolamines whereof at least one has a pk
a above 9 and another having a pk
a of 9 or less may also be used as disclosed in the Japanese patent applications laid
open to the public numbers 73949/61, 73953/61, 169841/61, 212670/60, 73950/61, 73952/61,
102644/61, 226647/63, 229453/63, US-P-4,362,811, US-P 4,568,634 etc.. The concentration
of these alkanolamines is preferably from 0.1 mol/l to 0.9 mol/l.
[0089] Suitable developing agents for the exposed silver halide are e.g. hydroquinone-type
and 1-phenyl-3-pyrazolidone-type developing agents as well as p-monomethylaminophenol
and derivatives thereof. Preferably used is a combination of a hydroquinone-type and
1-phenyl-3-pyrazolidone-type developing agent wherein the latter is preferably incorporated
in one of the layers comprised on the support of the photographic material. A preferred
class of 1-phenyl-3-pyrazolidone-type developing agents is disclosed in the published
EP-A 449340.
[0090] According to a preferred embodiment for continuous tone reproduction a mixture of
developing agents comprising an o-dihydroxybenzene, e.g. catechol, a 3-pyrazolidinone
e.g. a 1-aryl-3-pyrazolidinone and optionally a p-dihydroxybenzene, e.g. hydroquinone
the molar amount of the o-dihydroxybenzene in said mixture being larger than the molar
amount of the 3-pyrazolidinone, and the p-dihydroxybenzene if any being present in
a molar ratio of at most 5 % with respect to the o-dihydroxybenzene can be used. Other
type of developing agents suitable for use in accordance with the present invention
are reductones e.g. ascorbic acid derivatives.
[0091] The developing agent or a mixture of developing agents can be present in an alkaline
processing solution, in the photographic material or the image receiving material.
In case the developing agent or a mixture of developing agents is contained in the
photographic material and/or image receiving material, the processing solution can
be merely an aqueous alkaline solution that initiates and activates the development.
[0092] In the DTR process the photographic element is developed in the presence of a silver
halide solvent. Preferably used silver halide solvents are water soluble thiosulphate
compounds such as ammonium and sodium thiosulphate, or ammonium and alkali metal thiocyanates.
Other useful silver halide solvents (or "complexing agents") are described in the
book "The Theory of the Photographic Process" edited by T.H. James, 4th edition, p.
474-475 (1977), in particular sulphites and uracil. Further interesting silver halide
complexing agents are cyclic imides, preferably combined with alkanolamines, as described
in US-P 4,297,430 and US-P 4,355,090. 2-mercaptobenzoic acid derivatives are described
as silver halide solvents in US-P 4,297,429, preferably combined with alkanolamines
or with cyclic imides and alkanolamines. Dialkylmethylenedisulfones can also be used
as silver halide solvent.
[0093] The silver halide solvent is preferably present in the processing solution but may
also be present in one or more layers comprised on the support of the imaging element
and/or receiving material. When the silver halide solvent is incorporated in the photographic
material it may be incorporated as a silver halide solvent precursor as disclosed
in e.g. Japanese published unexamined patent applications no. 15247/59 and 271345/63,
US-P 4,693,955 and US-P 3,685,991.
[0094] The processing solution for use in the production of black-and-white photographs
in opaque security documents according to the present invention may comprise other
additives such as e.g. thickeners, preservatives, detergents e.g. acetylenic detergents
such as SURFYNOL 104, SURFYNOL 465, SURFYNOL 440 etc. all available from Air Reduction
Chemical Company, New York.
[0095] The DTR-process is normally carried out at a temperature in the range of 10°C to
35°C.
[0096] Further details about the black-and-white DTR process and also about the dye diffusion
transfer process and image receiving materials used therein are described in Research
Disclosure November 1976, item 15162.
[0097] The present invention will now be illustrated by the following examples without however
limiting it thereto. All ratios, percentages and parts are by weight unless otherwise
specified.
EXAMPLE 1
- Preparation of photographic element for use in the DTR process
[0098] A gelatino silver halide emulsion was prepared by slowly running with stirring an
aqueous solution of 1 mole of silver nitrate per liter into a gelatine solution containing
per mole of silver nitrate 41 g of gelatin, 1.2 mole of sodium chloride, 0.08 mole
of potassium bromide and 0.01 mole of potassium iodide.
[0099] The temperature during precipitation and the subsequent ripening process lasting
three hours was kept at 40°C.
[0100] Before cooling, shredding and washing 214 g of gelatin were added per mole of silver
halide. The washed noodles were molten and another 476 g of gelatin were added per
mole of silver halide during the chemical ripening. After ripening 285 g of gelatin
in the form of a 20 % aqueous solution were added to the emulsion per mole of silver
halide as well as hydroquinone in an amount such that after coating 0.9 g of hydroquinone
were present per m
2 and 1-phenyl-4,4-dimethyl-3-pyrazolidinone in an amount such that 0.21 g thereof
were present per m
2. The emulsion was coated at one side of a subbed water-resistant paper support consisting
of a paper having a weight of 110 g/m
2 coated at both sides with a polyethylene stratum at a ratio of 20 g/m
2 per side.
[0101] The emulsion was coated in such a way that an amount of silver equivalent to 1.5
g of silver nitrate was applied per m
2. The amount of gelatin corresponding therewith is 8.93 g/m
2 since the gelatin to silver nitrate weight ratio was 5.97.
- Preparation of image receiving material for use in the DTR process
[0102] One side of a paper support having a weight of 100 g/m
2 being coated at both sides with a polyethylene layer of 20 g/m
2 was coated after corona treatment at a dry coverage of 2.5 g/m
2 of gelatin and 1.3 g/m
2 of interference pigment from the following coating composition :
| carboxymethyl cellulose |
12 g |
| gelatin |
38.5 g |
| 3 % aqueous dispersion of colloidal Ag2S.NiS nuclei |
14 ml |
| 4 % aqueous solution of formaldehyde |
12 ml |
| aqueous dispersion of blue PALIOSECURE type EC 1408 (tradename) containing 30 % of
said blue pigment and 8 % of gelatin |
80 g |
| 12.5 % solution of saponine in ethanol/water (20/80) |
20 ml |
- Printing of the image receiving material with pattern of interference pigment
[0103] In the area lateron to be DTR-processed to form therein a portrait of a person being
owner of a passport, a guilloche pattern was gravure-printed using an ink having the
following composition :
[0104] 15 % dispersion of green PALIOSECURE type EC 1407 (tradename) in a cellulose nitrate
solution in liquid polyethylene glycol ether.
[0105] The printed ink pattern was dried at the air.
- Printing of the image receiving material with pattern of graphical and numerical
information using a blue non-iridiscent ink
[0106] The printing of said information was carried out in the background area having a
blue color due to the presence of said interference pigment PALIOSECURE type EC 1408
(tradename). The printing of the blue non-iridescent ink proceeded at such density
that there was no visible contrast at 90° inspection angle (being also the usual copying
angle) between the background and the thus printed area.
DTR-image formation
[0107] The above defined photographic element was image-wise exposed in a reflex camera
to obtain therein in the guilloche covered area a photograph (portrait) of the passport
owner.
[0108] The photo-exposed element was pre-moistened with a processing liquid as defined hereinafter.
[0109] The contact time of the photo-exposed element with said liquid was 6 seconds before
being pressed together with the image-receiving material as defined above. The transfer
processor employed was a COPYPROOF (registered trade name of AGFA-GEVAERT N.V.) type
CP 380. The transfer contact time was 30 seconds. In the image-receiving layer a positive
black-and-white (silver image) portrait of the photographed person was obtained.
| - Composition of the processing liquid: |
| hydroxyethyl cellulose |
1.0 g |
| Ethylenediaminetetraacetic acid tetrasodium salt |
2.0 g |
| Na2SO3 |
45.0 g |
| Na2S2O3 |
14.0 g |
| KBr |
0.5 g |
| 1-Phenyl-5-mercapto-tetrazole |
0.1 g |
| 1-(3,4-Dichlorophenyl)-1H-tetrazole-5-thiol |
0.02 g |
| N-methyl-ethanolamine |
45.0 ml |
| N-methyl-diethanolamine |
30.0 ml |
| Water up to |
1 l |
[0110] When viewed under an angle of 90° in daylight the color of the non-printed area around
the portrait was blue due the presence of uniformly distributed therein blue PALIOSECURE
type EC 1408 (tradename) . In the portrait area containing green PALIOSECURE type
EC 1407 (tradename) black silver was missing and the guilloche pattern had a bluish-green
color.
[0111] When viewing the document under an angle less than 45° the background area containing
blue PALIOSECURE type EC 1408 (tradename) changed to become yellowish. Under that
angle the graphical information and numerical information printed with said blue non-iridescent
ink became legible.
[0112] On copying the obtained document with a color copier (CANON CLC 500) the above defined
color changes were not reproduced in the obtained print. The guilloche pattern covering
the portrait area can hardly be seen in the obtained print, and the blue printed graphical
information is not copied.
EXAMPLE 2
- Preparation of image-receiving element for use in dye diffusion transfer process
[0113] An opaque polyvinyl chloride sheet having a thickness of 0.200 mm was after corona
treatment coated at one side with the following compositions for forming a subbing
layer and mordanting layer respectively :
| 1. Subbing layer coating composition |
| gelatin |
4 g |
| aqueous dispersion of blue PALIOSECURE type EC 1408 (tradename) containing 30 % of
said blue pigment and 8 % of gelatin |
200 g |
| ingredient A 40 % solution dispersed in aqueous medium |
250 ml |
| 5 % solution of siloxane compound in ethanol |
125 ml |
| 12.5 % solution of saponine in ethanol/water 20/80 |
20 ml |
[0114] Ingredient A is a polyester-polyurethane having the same chemical composition as
described in US-P 4,902,593, column 2, lines 64-68 and column 3, lines 1-8.
[0115] The coating composition was applied coated at a dry coverage of 0.4 g/m
2 of gelatin and 1.2 g.m
2 of interference pigment.
| 2. Coating composition of the mordanting layer |
| gelatin |
20 g |
| mordant M (20 % solution) |
250 ml |
| saponine (12 %) and wetting agent W (5 %) in water |
32 ml |
| aqueous 4 % solution of formaldehyde |
10 ml |
[0116] Mordant M on the basis of an epoxidized cationic polymer has the same composition
as described in US-P 4,902,593, column 7, lines 14-42.
[0117] The coating composition was applied at a dry coverage of 0.9 g/m
2 of gelatin.
[0118] The above defined image-receiving material was processed in combination with a photographic
dye diffusion transfer material as described in the Example of U.S. Pat. No. 4,496,645,
which material was exposed to reproduce thereon a portrait. The exposed material was
kept for 1 minute in contact with the above defined image-receiving material after
being led through a diffusion transfer apparatus COPYPROOF CP 38 (tradename of Agfa-Gevaert
N.V. Belgium) having in its tray the following basic processing liquid :
| sodium hydroxide |
25 g |
| sodium orthophosphate |
25 g |
| cyclohexane dimethanol |
25 g |
| 2,2'-methylpropylpropane diol |
25 g |
| N-ethylbenzene-pyridinium chloride |
0.5 g |
| distilled water up to |
1000 ml |
[0119] After leaving the processing tray the image-receiving sheet was led through a second
tray containing an aqueous 5 % solution of the already mentioned wetting agent W corresponding
with the following formula : iso-nonyl-phenoxy-(CH
2-CH
2-O)
9-H and potassium iodide (ref. EP 0250657).
[0120] After drying the processed sheet material it was laminated as described in US-P 4,902,593
to obtain a sealed I.D. card.
EXAMPLE 3
[0121] According to Example 3 the interference pigments were applied uniformly in a mordanting
layer of an image-receiving material suited for use in a dye diffusion transfer process.
- Preparation of the image-receiving element
[0122] An opaque polyvinyl chloride sheet having a thickness of 0.200 mm was after corona
treatment coated at one side with the following compositions for forming a subbing
layer and mordanting layer respectively :
| 1. Coating composition of the subbing layer |
| gelatin |
20 g |
| ingredient A 40 % solution dispersed in aqueous medium |
250 ml |
| 5 % solution of siloxane compound in ethanol |
125 ml |
| 12.5 % solution of saponine in ethanol/water 20/80 |
20 ml |
[0123] The coating composition was applied coated at a dry coverage of 0.4 g/m
2 of gelatin.
| 2. Coating composition of the mordanting layer |
| gelatin |
12 g |
| aqueous dispersion of blue PALIOSECURE type EC 1408 (tradename) containing 30 % of
said blue pigment and 8 % of gelatin |
100 g |
| mordant M (20 % solution) |
250 ml |
| saponine (12 %) and wetting agent W (5 %) in water |
32 ml |
| aqueous 4 % solution of formaldehyde |
10 ml |
[0124] The coating composition was applied at a dry coverage of 0.9 g/m
2 of gelatin, and 1.3 g/m
2 of interference pigment.
EXAMPLE 4
[0125] Example 3 was repeated with the difference that the interference pigments were applied
uniformly in a gelatin top coat covering the mordanting layer. The dried top coat
contained 0.5 g/m
2 of gelatin and 1.3 g/m
2 of interference pigment.